Catalyst containing aluminum, titanium tetrahalide, and alkali metal fluoride and olefin polymerization therewith



[ n e St te P t t-* c i nvsr CONTAINING ALUMINUM, "in'rg r FLUORIDE AND LEFIN POLYMERIZ QTION.

2325,410. Ratented 16, 1960 thisinvention to polymerize propylene and higher a-mono olefins in the presence of an improved catalytic mixture wherein the formation of-relatively low molecular weight polymers is substantially and unexpectedly reduced.

It is an object ofthis invention to provide a novel and 7 improved process for polymerizing propylene and higher Harry W. Coover,.J1-'., Kingsp'ort, Tenn assignor to East-- man Kodak Company, Rocliester, N.Y., a corporation ofNewJersey V f I No Drawing; Application April 3, 1958 V 1 Serial No. 726,036

This invention relates to a new and improved polymerization process and is particularly concerned with the use of a novel catalyst combination for preparing high molecular weight solid polyolefins, such as polypropylene, of high densityand crystallinity, In a particularaspect the invention is concerned with the preparation of polyproe pylene and higherpolyolefins having ahigh crystallinity' and a high density using aparticular catalyst combination which has unexpected catalytic :activity.

u-monoolefins and in doing so to overcome disadvantages of earlier procedures. ,It is a particular object of this invention to provide a novel and improved process for polymerizing propylene in the presence of an improved catalyst composition containing aluminum and a titanium tetrahalide. As' a result of the use of this improved catalyst composition unexpectedly improved yields of solid, I

dense, crystalline polymer are obtained without the con comitant formation of substantial amounts of lower molecular weight polymer. Other objects of this invention will be apparent from the description'and claims which follow. 7 s

The above and other objects are attained by means of this invention, wherein a-monoolefins, ieither singly-or in admixture, are readily polymerizedto; high molecular weight solid polymers by elfectingthe polymerization in Polyethylene, has heretofore ;been,.prepared iby 7 pressure processes to give relatively flexible polymers havinga rather high degree: of chain branching and adensity considerably, lower ,;than thetheoretical density.

Thus, pressures of theorder of 500 atmospheres or more and usually ofithe order of lOOOdSOO atmospheres are commonly employed, It hasbeen found that more dense polyethylenes can he produced by, CQ Ta j-Caa1yst com-,

binations, to give polymers which have; very little chain branching and a high degree ,of crystallinity, The exact reason why certain. catalyst ,combinations give these highly dense and highly crystalline polymers: is not predictable, since relatively minor changes in the'catalyst combination often lead to liquid polymers rather than the desired solid polymers,

the 'pr'esence of an unactivated or a preactivated' aluminum-titanium te'trahalide catalyst compositionjcontaining containing an alkali metal fluoride. The significantly.

improved yields ofthe vcrystalline polymers; produced with' the abovecatalyst were completely unexpected.- The inventive process can be carried out in liquid phase in an readily understood. -Furthermore, the activity of the catalysts ordinarily depends, upon certain specific'catalyst'. combinations, and .the results areordinarily highly un-' In my copending applicationSerialNOaSSQQB, filed I January 17, 1'95 6, of which this application is a continuation-in-part,,. thereis described. the polymerization of d monoolefins' to produce dense highly crystalline poly mers by heating said 'morioolefins in; the presenceof a mixture of aluminum anda titanium tetrahalide. Also in my copending ,application Serial No. 711,139, filed January 27, 1958,- which is also a continuation impart of application Serial No. 559,536, there is described the polymerization of a-monoolefinsto nform dense crystalline polymers by polymerizing said monoolefins in the presence asast dzaa 1 't .v d; a t p t uia qata t agre .bY-h t a atu e of l um at tan umfi rah ideiatheab a p l er ab :hYQr qarbQa- :Thi l tt ma lys s e te m d are ctivated. a a r tqaa lt ze fQan s ta s n termed an unactivated catalyst. The preactivated catalyst 1 as: 9 011 =t0i 19 1 P l P cl d w pr results 'W i --Q P3- I ithhe n ac tedvata t- 'hl or; yn rizina wpy n h her g-mqng a i onn n e CIYQ1HQQ1PO1YIIIES E H weve w n the activated'and preactivated catalysts are used to poly-' amounts of rrel ativelyglow molecular? {weight polymers hi e eith r. gr,eases, ils or rubbery products: 0b;

ht, dense crystalline- "glecu a li eigh 1 ,and' it' ion of me purposes or inert organic liquid and preferably anin'ert liquid hydro-f carbon vehicle, but in some instances the process is operated without a solvent. Theprocess proceeds with ex' celle'nt results over-a temperature range of from 20f .C.

to '200 C. although it "is preferred to operate within the range of from about-55 C. to about C. Likewise; the reaction pressures may be'varied'widely from about atmospheric pressure to very high pressuresof the orderof 20,000 p.s'.i. or higher. I A particular'advantage ofthe invention is that pressures of the order of 30-1000 0 p'.'s.i. give excellent results, and it is not necessary'to employ the extremely high pressureswhich were necessary heretofore. The liquid vehicle employed is desirablyone' which serves as an inert liquid medium.

The invention is of particular importance in the prep aration of highly crystalline polypropylene although it can be used forpolymerizing-mixture's of ethylene and propylene as well as other -monoolefins containing upto -l0 carbon atoms. The results'obtained by polymerizing the'various olefins are quite unexpected. The crystallinity of the polymer as well as the average molecular weight of the product are substantially and unexpectedly improved, The high molecular weight, high density poly mers of this invention are insoluble in solvents at ordinary temperatures but are partially soluble in such solvents as xylene, toluenej or tetralin" atelevateditemperaitures.

,These solubility characteristics make it possible to carry out the polymerization process under conditions wherein 'the polymer formed is soluble in-the reaction medium during the polymerization and can be precipitated therefrom by lowering the temperature of the resulting mixture. The polypropylene producedby practicing this invention has 'a 'soft'ening' point above C. and a densityof 0.91' andlhigher, Usually the density of the 'polypropyl'ene-is of the order of 0.91 to 0.92.

The polyproplylene and ther polyolefins'prepared in ace-5,410

3 elasticity and rigidity. Fibers of high strength can be spun from the molten polypropylene obtained according to this process. Other poly-u-olefins as well as copolymers of ethylene and propylene can also be prepared in accordance with this invention.

As has been indicated above the improved results obtained in accordance with this invention depend upon the particular catalyst combination. Thus, one of the components of the catalyst is aluminum and another com" ponent is a titanium tetrahalide wherein the halogen is selected from the group consisting of chlorine, bromine and iodine. The third component of the catalyst composition is an alkali metal fluoride. The preferred fluoride is sodium fluoride, but potassium fluoride and lithium, fluoride can be used, if desired.

The limiting factor in the temperature of the process appears to be the decomposition temperature of the catalyst. Ordinarily temperatures from 55 C. to 150 C. are employed, although temperatures as low as 20 C. or as high as 200 C. can be employed if desired. Usually, it is not desirable or economical to eifect the polymerization at temperatures below 20 C., and the process can be readily controlled at room temperature or higher which is an advantage from-the standpoint of commercial processing. The pressure employed is usually only suflicient to maintain the reaction mixture in liquid form during the polymerization, although higher pressures can be used if desired. The pressure is ordinarily achieved by pressuring the system with the, mono.-, rner wherebyVaclditionalmonomer dissolves in the reaction vehicle as the polymerization progresses. The catalystmixture is readily soluble in the usual organic liquid. ve-. hicles andhence the uniformity of reaction can be readily controlled.

The polymerization embodying the invention can be, carried out batchwisev or in a continuous flowing stream process. The continuous processes are preferred for eco;

ployed in autoclave type reactions.

,4 cause the polymer dissolves in the reaction medium and results in a very viscous solution.

The titanium tetrahalide in the catalyst is usually employed in an amount of from 0.1 to 45 parts by weight per part of aluminum metaL'and weight ratios of titanium tetrahalide to metal fluoride within the range of 1:05 to 1:2 are preferred. However, it will be understood that ratiosfoutside these ranges can be used in practicing this invention. The polymerization time can be varied as desired and will usually be of the order of from 30 minutes to several hours in batch processes. Contact times of from 1 to 4 hours are. commonly em- When a continuous process is employed, the contact time in the polymerization zone can also be regulated as desired, and in some cases it is not necessary to employ; reaction or contact times much beyond one-half to one hour since a cyclic J system can be employed by precipitation of the. polymer and return of the vehicle and unused catalyst to: the: charging zone wherein the, catalyst; can be replenished and. additional monomer introduced.

The organic vehicle employed can be an aliphatic alkane. or cycloalka-ne such as. pentane, hexane, heptane 7 should be=liquid under the-conditions of reaction. and relaxnomic reasons, and particularly good results are obtained; i

using continuous processes wherein a polymerization mix; ture of constant composition is continuously and progres; sively introduced into the polymerization Zone and the mixture resulting from the polymerization is continuously and progressively withdrawn from the polymerization zone at an equivalent rate, whereby the relative concentration of the various components in the polymerization zone remains substantially unchanged during the process. This results in formation of polymer of extremely uni; form molecular weight distribution over a relatively.- narrow range. Such uniform polymers possess distinct advantages since they do not contain any. substantial amount of the low molecular weight or high molecular weight formations which. are ordinarily found in polymers prepared by batch reactions.

In the continuous. flowing stream process, the temperature is desirably maintained at a substantially con? stant value within the preferred range in order to achieve the highest degree of uniformity. Since it is desirable to employ a solution of the monomer ofrelatively high concentration, the process is desirably. effected under a pressure of from 30 to l000 p.s.i. obtained by pressuring the system with the monomer being polymerized. The amount of vehicle employed can be varied over rather wide limits with'relation to the monomer and catalyst" mixture. Best results are obtained using a concentration of catalyst of from about 0.l% to about 2% .by weight based on the weight of the vehicle. Theconcentratiou of the monomer in the vehicle will vary rather widely depending upon the reaction conditions and will usually range from about 2 to, 50% by Weight or preferably from about 2 to about 10% by weight based on the. weight of the vehicle. Concentrations of monomer in the vehicle of.- about 3 -7% by weight are commonly employed. Higher concentrations of monomer ordinarily increase the rate of-polymerization, but concentrations above, 5-,1Q%-b .weigh i rel ord nari y l d sirablebs:

tively inert. 'Fhe-hydrocarbon-liquids are desirablyemployed; Other solventswhichcan be usedincludeethyl benzene, isopropyl benzene, ethyl 'toluene, n-propyl' benzene, diethyl' benzenes, monoandfldialkyl naphthalenes, n-octane, isooctane, methyl cyclohexane, andany ofthe other well-knowninertliquid hydrocarbons;-

The polymerization ordinarily'is accomplishedb y'me'rely admixing the components of the polymerization mixture which is then adjusted to the reaction temperature. The more elevated temperatures can be used to increase the solubility of polymeric product in the; vehicle; When the highly uniform polymers are;desired emp loying the continuous process wherein the relative proportions of the variouscomponents are maintained'substantially'constant, the temperature is desirably controlled; within a relatively narrow range. This is readily accomplished since the solvent vehicle forms a high-percentage of the polymerization mixtureandhencecan be; heated or cooled to maintain the temperature asdesired.

A particularly effective catalyst for polymerizing propyl= ene andother a-monoolefinsin accordance with thisinvention is a mixture of aluminum; titanium tetrachloride and sodium' fluoride. The importance of the sodium fluo- 7 ride in this reaction mixture is evident from the factthat tal mitt i t l au f m h lide rehe diq -aper odlofffltne ryiflz p a o tm hwttoasv s a ially, q erper cdaQt'ffimaiame: a

sane polymerizable monomer, such; as.v ethylene: propylene and highermonooleiins.{'Tmperaturesioi 50fi C. up to about 300 C. areusuallysufiicientforithepre w s co cted, to e ervo q ntaininu propylene at 1.

. P -i-s- :nefiemp ure n70? c. n

activatiomand contact times froni' 5:?minutes' to e l 48 hours can be used. Suitable proceduresfior preparing preaetivated mixtures of aluminum, and titanium tetra: halide are described in my copendiiig applicationsSerial No. 559,536 and Serial No. 711,139.. The: catalytic mixture that is formed as a result of the preactivationof aluminum and titanium tetrahalide' can be'termed a reaction, product of aluminum and titanium itetrahalide. vThis mixture along with the alkali metalfluoride described above is outstandingly etiectivefor polymerizingpropylene and higher monoolefins while at the same time reducing substantially the amount of low molecular weight poly mers formed during the reaction. 'Ihealuminum that is employed in the catalyst mixture is preferably in flake or finely-divided form foroptimirm'activity, rapid polymerization and high yield of polymer but actually any form of aluminum metal can be u'sedi'n the process. When a granular aluminum of commerce is'used it is desirable to clean the surface of the granuleswith an acid oracid mixtures such as a mixture of nitric and hydrofluoric acids or with a base for optimum results. However, the cleaning of the aluminum is notabsolutely essential to the invention. Titanium tetrachloride is the preferred titetrahalide although titanium tetrabromide as well as titanium tetraiodide can be used.

The invention is illustrated by the following examples ofcertain preferred embodimentsthereof. v

' Exan'ipl eiu. In a nitrogen filled dryi box, a 'preactivated catalyst which had been prepared by reacting 0.5 g. of aluminum and 3.5g. of 'tan1um tetrachloride in mineral oil at 140 in a 300 ml. stainless steel autoclave. The autoclavewas hours; at these conditions. it l a'cylinderofpropylene. 1 heen oft e aci b l PsnQd; g eib Wasopehed andthe contents were treatedwithethanol, strong aqueous sodium hydroxidesolutiomand finally water. The prode uct'was 2 1 -g.':of polypropylene. trom which a highly 'crystallineires'idue weighi g g.' was obtained upon The procedure of except that thetheptane was replaced;withmineral oiland the tent:

perature was raised to 100.? C. andthe pressure of propylene was raised-"to p.s. i. The -yield o f'highly crystalline product was.19.5 g.;: r e

,-nramp a7' 77 p I The procedure of Example 6fwas repeated except that 1.7 'g. oftitanium tetrachloridewasused- The product was ,27 g. of polymer from which 22g. of highly crystalline polypropylene was obtained upon extraction.

' Example 8 1 v The procedure ofExample 5 was repeated at p.s.i. propylene pressure and increasing the amount of sodium fluorideto 5.0 g. The product .was 28 g. of polymer I which gave a highly crystalline residueweighing 23 g.

. .35' 1 C..-for 4 hours, was placed with 2.3 g; of sodlum fluoride 1 a V "Exdmple39f. i The'procedure of Example 5' 'was repeated to obtain increased yields ofcrystalline polymer using as monomers l-butene,"4-methyl 1 penten styrene allyl benzene, vinyl cyclohexane' and fluorstyrene. 1

Elim'inationof alkali .tali fluoride from the catalysts .in the above'examples resul-tis" in th'i joduction of large amounts *of oily; low' 'molecularwe ight polymers and lowyieldsl ("1 to jjgrams) ;'solid crystalline polymers.

of the poly-propylene product wa'sffil g Extraction of of highly crystalline,polypropylenejhaving aglensitylof 0.9l8and aninherent viscosityvof 2.30.

5 i Example 2 I i The procedureof Example 1 was repeated except that the mixture was rocked at 150 C. for eight hours. The

. product was 34 gjof'polymer, which upon extraction left ride were used. The product which weighed 18 g. gave The polymers can b'eusjedas blending agents with relati'velyf'r'rior'eflexible polyhydrocarbons to give any desired a highly crystalline. polypropylene residue, upon. 'extrae- 1 tion, which weighed 13.5 g.; density 0.912; inherent viscos-- ity 2.13.

Example 4 r The procedure of Example 1 was followed at a 70 1 in order to obtain a commercial product.

-C. polymerization temperature using 100 of 3amethyljl-butene-l instead of propylene. The product was 23 g.

-of polymer which yielded after extraction a 14 g. residue .of highly crystalline poly-3-methyl-l-butene. By 1 ;;same procedure 4-methyl-l-pentene was polymerized to :.a highly crystalline polymer in good yield,

7 Example 5,

3.2.5 g. of titanium tetrachloride was placed with 2.3 g.-

...--of sodium fluoride ina 500 ml. pressure bottle.' One i lhuudred milliliters-of heptane was added and the bottle carbons.

.hinatidnlwhose improv I been predicted; The1 polfyiners thusobtainedcan be ex Thusf by" means 'of inventiompolyolefins such as polypropylene are readily produced using a catalyst comeiiiectivene'ss'could not have truded; mechanicallyf milled, cast or molded as desired.

combination of prop'erties'fThe' polymers can also be blended with antioxidants, stabilizers, plasticizers, fillers, pigments, and the .like, or mixed with other polymeric materials, waxes and thelike. i In general, the polymers embodying this invention canbe treated in similar manner to those'obtained by other processes.

From the detailed disclosure of this invention it is quite apparent that in this po lymerization procedure a novel catalyst, not suggested in priorart polymerization procedures, is employed. As a result of the use of this novel catalyst it is possible to produce polymeric hydrocarbons, particularly polypropylene, having properties not heretofore obtainable. in the presence of catalyst combination within the scope of this invention is substantially free of rubbery and oily polymers and thus it is not necessary to subject such polypropylene of this invention to extraction procedures Also polypropylene produced in accordance with this invention possesses unexpectedly highcrystallinity, an unusually high softening point and outstanding thermal stability. Such polypropylene also has a very highstiifness as a result ofthe unexpectedly high crystallinity. The properties imparted to polypropylene prepared in accordance with this invention thus characterize and distinguish this poly- V i e propylene from polymers prepared by prior art polymeria The reaction product o=f0.5 g. of aluminum metal with I zation procedures.

The novel catalysts defined above can be used to pro duce high molecular weight crystalline polymerichydro- The molecular weight of the polymers'can be;

For example, polypropylene prepared varied over some range" By irit'rb'ducing hydrogen to the polymerization reaction. 1 Such hydrogen 'can be introduced separately or in admiitm'e With the olefin monomer. The polymers produced in accordance with this invention can be separated fi'ofri polymerization catalyst bys uitable extraction prseedfires, fof ekample s5; washing with water or lower aliphatic alcohols siich as methanol. The catalyst compositionshave been described above as being eficctive primarily for "the polymerization of a monoolefins. These catalyst composi-tions can, however, be used for polymerizing other a-olefins, and it is not necessar to limit the process of the ifiVEflt1UH 1IO'Hl'OHO olefins. Other a-olfi'iis that can be used are butadiene, isopr'eiie, 1,3-pentadiene and the like.

The diluents employed in praeticing this invention can be advantageously purified prior to use'inthe polymerization reaction by contacting the diluent, for example in a distillation procedure or otherwise, with the polymerization catalyst to remove undesirable trace impurities. Also, prior to such purification of the diluent the catalyst can be contacted advantageously with 'polyme'rizable a-mono'ol'efin.

Although the invention has been described in considerable detail with reference to certain preferred embodimerits thereof, variations and modifications can be'efte'cted within the spirit and scope or this invention as described hereinabove and as defined in the appended claims.

I claim: 7

1. In the polymerization of a-monoolefinic hydrocarbons containing from 3-10 carbon atoms to form solid crystalline polymer, the improvement which comprises catalyzing the polymerization with a catalytic mixture consisting essentially of aluminum and a titanium tetrahalide selected from the. group consisting of tetrachloride, tetrabromide and tetraiodide, in a weight ratio of 1:0.1 to 1:45 and a weight ratio of titanium tetrahalid'e and a fluoride of an alkali metal selected from 'the' group consisting of sodium, potassiumand lithium Within the range of 120.5 to 1:2; l V a 2. In the polyme'zation of propylene to form solid crystalline polymer, the improvement which comprises effecting the polymeri zation in liquid dispersion in an inertorganic hydrocarbon solvent and in thepres'enoe'of a catalytic mixture consisting essentiallyof an activated aluminum-titanium tetrahalide, selected from the group consisting of tetrachloride, tetrabromide and'tetr'aiodide, in a weight ratio of 120.1 to 1:45 and a weight ratio of titanium tetrahalide and a fluoride of an alkali metal selected from the group consistingof sodium, potassium and lithium, Within the range of 110.5 to ,1 :2.

3. In the polymerization of propylene to' form solid crystalline polymer, the improvement which comprises effecting the polymerization in liquid dispersion m an inert organic hydrocarbon solvent and in the presence'of' a catalytic mixture consisting essentially of' an activated v a ea ly'tic' mixture consisting essentially 'of activated aluirl'ihuiri-titanium tetrachloride in a weight ratio of 1:01 to 1:45 and a Weight ratio of titanium tetrachloride and sod'iumfluoride Within the range of l:' 0.5 to 1:2. I

5. The method according to claim 4 wherein the poly menization is eifected at a temperature of to C; and a pressure not exceeding 1000 p.s.i. '6. As a composition of matter, a polymerization catalyst consisting essentially of aluminum and a titanium tetrahalide selected from the group consisting of tetrachlo fide, tetrahromid'e', an'd tetraiodide in a weight ratio of 110.1 to 1:45 and a Weight ratio of titanium tetrahalide and a fluoride of an alkali metal selected from the group consisting of sodium, potassium and lithium within the ra ge of 150.5 'to 1:2.

7 As a 'contposition'of matter, a polymerization cata lyst consisting essentially of "an activated aluminum= titanium tetrachloride in a Weight ratio of 110.1 to 1:45 and a Weight ratio of'titanium tetrachloride and a fluoride of an alkali metal seleetedifrom the group consisting of sodium, potassium and lithium Within the range of 1:05 to 1:2.

8; As acomposition of matter, a polymerization cata lyst consisting essentially of an activated aluminum; titanium tetrachloride in a weight ratio of 1:0.1 to 1:45 and -a weight ratio of titanium tetrachloride and sodium fluoride within the range of 1:0.5 to1:2.

References Cited in the file ofthis patent Y UNITED STATES PATENTS 2,834,768 Friedlander May 13, 1958 2,840,551 Field r;...' June 24, .1958 2,844,615 Ziegler July 22, 1958 FOREIGN PATENTS 1,132,506 France 'Nov. 5, 1956 1,137,020 France Jan. 7, 1957 1,137,084 France Jan. 7, 1957 1,144,710 France Apr."29, 1957 783,487 Great Britain Sept. '25, 1957 794,785 Great Britain May 7, 1958 

1. IN THE POLYMERIZATION OF A-MONOOLEFINIC HYDROCARBONS CONTAINING FROM 3-10 CARBON ATOMS TO FORM SOLID CRYSTALLINE POLYMER, THE IMPROVEMENT WHICH COMPRISES CATALYZING THE POLYMERIZATION WITH A CATALYTIC MIXTURE CONSISTING ESSENTIALLY OF ALUMINUM AND A TITANIUM TETRAHALIDE SELECTED FROM THE GROUP CONSISTING OF TETRACHLORIDE, TETRABROMIDE AND TETRAIODIDE, IN A WEIGHT RATION OF 1:0.1 TO 1:45 AND A WEIGHT RATION OF TITANIUM TETRAHALIDE AND A FLUORIDE OF AN ALKALI METAL SELECTED FROM THE GROUP CONSISTING FO SODIUM, POTASSIUM AND LITHIUM WITHIN THE RANGE OF 1:0.5 TO 1:2. 